Polyglycidyl compounds containing n-heterocyclic structure

ABSTRACT

The polyglycidyl compounds according to the invention can be manufactured by reacting epihalogenohydrin with compounds of the formula IV   OR THE FORMULA V   in which 1.) n denotes 2, 3 or 4, 2.) A represents a 2-valent, 3-valent or 4-valent organic radical which either contains a Nheterocyclic or cycloaliphatic ring or 2 N-heterocyclic rings or 2 phenylene rings, 3.) either B denotes the -CH2.O.CO- radical and m denotes the number 1, or B denotes the radical and m denotes 0, and 4.) R1 represents a divalent radical, which contains at least one hydrantoin ring or uracil ring. During the reaction hydrogen halide splits off. From curable mixtures containing polyglycidyl compounds according to the invention and a curing agent such as hexahydrophthalic anhydride or phthalic anhydride are obtained products with good mechanical and electrical properties.

United States Patent [1 1 Habermeier et al.

[ Aug. 19, 1975 POLYGLYCIDYL COMPOUNDS CONTAINING N-HETEROCYCLICSTRUCTURE [75] Inventors: Jiirgen Habermeier, Pfeffingen;

Hans Batzer, Arlesheim; Daniel Porret, Binningen, all of Switzerland[73] Assignee: Ciba-Geigy Corporation, Ardsley,

22 Filed: June 19, 1973 211 App]. NOJ 371,449

[30] Foreign Application Priority Data June 23. 1972 Switzerland 9528/72[52] US. Cl. 260/309.5; 260/2; 260/37;

260/57; 260/69; 260/72; 260/78; 260/257; 260/260 [51] Int. Cl.. C07d49/32; C07d 51/20; C07d 51/30 [58] Field of Search 260/309.5

[56] References Cited UNITED STATES PATENTS 3629.263 l2/l97l Batzer etal 260/257 Primary E.raminerHenry R. Jiles Assistant li.\'z. minerC. M.S. .laisle Attorney, Agent, or Firm-Vincent J. Cavalieri [57] ABSTRACTThe polyglycidyl compounds according to the invention can bemanufactured by reacting epihalogenohydrin with compounds of the formulaIV or the formula V in which 1.) n denotes 2, 3 or 4, 2.) A represents a2- valent, 3-valent or 4-valent organic radical which either contains aN-heterocyclic or cycloaliphatic ring or 2 N-heterocyclic rings or 2phenylene rings, 3.) either B denotes the Cl-l .O.CO-- radical and mdenotes the number I, or B denotes the radical cit-o eu o hydride areobtained products with good mechanical and electrical properties.

5 Claims, No Drawings POLYGLYCIDYL COMPOUNDS CONTAINING N-HETEROCYCLICSTRUCTURE The invention relates to new polyglycidyl compounds containingN-heterocyclic structures, a process for their manufacture and theiruse.

standards set with regard to mechanical and electrical properties.

The subject'of the invention are new polyglycidyl compounds containingN-heterocyclic structures, of the general formula I in which a and b areidentical or different and denote either 0 or 1, and in which R denotesa hydrogen atom or a methyl group and R denotes a nitrogen-free, 2-valent radical which is necessary to complete a fivemembered orsix-membered unsubstituted or substituted ring, or of the generalformula III (III) in which 1. either B denotes the -CI-I .O.CO- radicaland m denotes the number 1, or B denotes the radical /CH O cu -o andmdenotes O, and 2. R has the above meaning.

In the formula I, A can represent one of the following organic moleculargroups:

| C H OH CH in which 1. n denotes 2, 3 or 4, 2. A represents a 2valent,3-valent or 4-valent organic radical which either contains aN-heterocyclic or cycloaliphatic ring or 2 N-heterocyclic rings or 2phenylene rings, and 3. R represents a divalent radical of the formulaII CH CH In the formula ll, R can denote one of the radicals In such acase, the polyglycidyl compounds according to the formula I or formulaIll are substances containing hydantoin rings.

R can, however, also represent one of the following divalent radicals:

or the formula V in which A, R, B, n and m have the abovementionedmeaning with epihalogenohydrin, hydrogen halide being split off. Insteadof epihalogenohydrin, methylepihalogenohydrin can also be employed. Inthat case, polyglycidyl compounds are obtained which are slightlymodified by the methyl groups introduced into the molecule. Preferably,epichlorohydrin is employed.

The process according to the invention is advantageously carried outwith azeotropic removal of the water in the presence of a hydrogenhalide acceptor. As such it is possible to use, for example, alkalimetal hydroxide, most simply sodium hydroxide in an equivalent amount orin slight excess (5 30%). If desired, a catalyst is also employed, forexample a quaternary ammonium halide, such as tetramethylammoniumhydroxide, teetraethylammonium bromide or benzyltrimethylammoniumchloride.

It is surprising that the process according to the invention can becarried out without complications. Given the presence of the numerousactive H atoms in the reaction mixture and the accumulation of theepoxide groups in the molecule of the resulting end product of theformula I or III, complications due to undesired polyaddition andpremature crosslinking were to be expected.

The starting substances of the formula IV or of the formula V for themanufacture of the polyglycidyl compounds according to the invention arealso new. They are substances which always contain at least 2 (namely n)secondary hydroxyl groups. In addition, they either contain n NH groupsof a N-heterocyclic ring and n primary hydroxyl groups.

The manufacture of these new polyols of the formula IV or of the formulaV takes place, in the former case, by reaction of appropriate diepoxide,triepoxide or tetraepoxide compounds with H-heterocyclic substances ofthe formula in which R and a are defined as above, to give thecorresponding adduct in a manner which is in itself known,

5 there being about 2 NH groups in the reaction mixture per 1 epoxidegroup.

In the latter case, in which the substances of the formula 1V or of theformula V also contain primary hydroxyl groups in addition to thesecondary hydroxyl groups, an identical adduct to that in the first caseis initially manufactured as an intermediate product. In a 2nd stage,the NH groups contained in this adduct are then reacted further withethylene oxide or propylene oxide in a known manner to give theparticular primary alcohol.

The following may be mentioned as examples of polyepoxide compoundswhich are suitable for use as starting products for the polyols of theformula IV: 1- glycidyl-3-(glycidyl-2'-oxy-n-propyl)-5,5-dimethylhydantoin, 1-glycidyloxymethyl-3-glycidyl-5,5-dimethylhydantoin, 1,1 '-methylenebis-( 3-glycidyl-5,5-dimethylhydantoin), 1,3-diglycidyl-5,5- dimethylhydantoin, 2,2,6,6-tetra( glycidylcarboxyethyl)cyclohexanone, bisphenol-A diglycidylether or polymeric derivatives thereof. (As regards the polymericderivatives of bisphenol-A diglycidyl ethers, it should additionally benoted that for practical purposes appropriate polymer mixtures withdegrees of polymerisation of up to about 5 are concerned).

As polyepoxide compounds which are suitable for use as starting productsfor the polyols of the formula V, the following should be listed asexamples: 3,4- epoxycyclohexylmethyl) -3, 4- epoxycyclohexanecarboxylateand 3-(3,4-epoxycyclohexyl)-2,4- dioxaspiro-(S ,5 )-9, l-epoxyundecane.

The following N-heterocyclic substances are examples of reactionpartners for these polyepoxide compounds in the manufacture of the abovepolyols: 5,5- pentamethylenehydantoin, 5,5-dimethylhydantoin, 5-isopropylhydantoin, 5,5-diethylbarbituric acid, 1,1- methylene-bis-( 5,5-dimethyl-5,6-dihydrouracil 1,1 methylene-bis-( 5,5-dimethylhydantoin), 1,1 methylene-bis-(5-isopropylhydantoin),6-methyluraci1, 5,5-dimethyl-6-isopropyl-5,6-dihydrouraci1 and 1,2-bis-( 5 ,5-dimethylhydantoinyl-3 )-ethane.

These new polyols which may contain NI-I groups are viscous or solid, inmost cases pale yellow-coloured, substances. If these are derived frompolymeric bisphenol-A diglycidyl ethers, the reaction with theepihalogenohydrin leads either to polyglycidyl compounds of the formulaI which still contain, unchanged, the OH groups originating from theinitial diglycidyl ethers, or to polyglycidyl compounds which containadditional epoxide groups produced by reaction of these originallypresent OH groups with epihalogenohydrin. Furthermore, intermediatestages are also possible. The degree of reaction of the original OHgroups results essentially from the amount of the epihalogenohydrin andcaustic alkali in the reaction mixture. Usable polyglycidyl compounds ofthe formula (1) according to the invention are also obtained by startingfrom compounds of the formula IV in which the radical A denotes themolecular group of the formula or the molecular group of the formula OH1 to 8 Starting substances for these special compounds of the formula IVare again the diglycidyl ethers of resorcinol or of polyetherscontaining several resorcinol structures.

The polyglycidyl compounds according to the invention, of the formula Iand the formula III, are solid or liquid, mostly pale yellow-coloured,substances. The special feature of these substances is that they containa relatively large number of glycidyl groups per molecule. They haveepoxide contents of between about 3.0 and 8.0 mols/kg of resin and can,together with curing agents, such as dicarboxylic acid anhydrides,easily be converted into curable mixtures at temperatures of 60 C.Hexahydrophthalic anhydride and phthalic anhydride are particularlysuitable as curing agents.

The curing of these mixtures, which is a further subject of thisinvention, in general takes place at temperatures of 80 to C. It canalso be carried out stepwise at different temperatures. Ultimately,mouldings of high mechanical and electrical quality are obtained. Thecurable mixtures according to the invention are in particular suitablefor use as compression moulding compositions and casting resins. Inprinciple, they can also be used as lacquer resins and laminatingresins.

For the manufacture, modification or processing and the like, everythingknown to the expert from publications and relevant patent specificationson an extensive scale applies to the mixtures according to theinvention.

In the examples which follow, parts denote parts by weight and thepercentages denote percentages by weight. The relationship of parts byvolume to parts by weight is as of ml to g.

A. MANUFACTURING EXAMPLES Manufacture of the Starting Substancesaccording to the Formula IV or V EXAMPLE A Adduct of5,5-dimethylhydantoin and 1,1 '-methylene-bis-(3-glycidyl-5,5dimethylhydantoin) 256 g of 5,5-dimethylhydantoin (2 mols)and 1.6 ml of 40% strength aqueous tetramethylammonium chloride solutionare heated to 170C in a glass apparatus equipped with a stirrer,thermometer and reflux condenser and the resulting melt is stirred. 380g of 1,1- methylene-bis-( 3-glycidyl-5 ,S-dimethylhydantoin) (5 .0equivalent of epoxide) are added over the course of 1 hour, whilststirring. 3 hours later, the residual epoxide content is only 0.14equivalent/kg. The mixture is stirred for a further 5 hours at C and theadduct is poured out onto a metal sheet. A solid, clear, brittle mass ofsoftening point 1 16C is obtained in quantitative yield. The residualepoxide content is only 0.048 equivalent/kg (corresponding to 98.3%conversion).

The content of NH groups in the 3-position of the N-heterocyclic ring is0.17 equivalent/kg (corresponding to a conversion of 94.3% of theory).Accordingly, the product predominantly consists of:

C H T H c 3 H C CH o 3 I I I .'l H N N-cH -cH-cH o -OCH2--(II'H--CH2 N NH Y OH CH OH Y o o C H 3 H C CH 3 H c c H 3 H 0 1 ,CH "3 0 o 3 I N-N NH2C-('IHCH2-N N CH2 N N -CH2CHCH2N N -H Y Y Y 0 O o 0 EXAMPLE B EXAMPLEC Adduct of 5,5-dimethylhydantoin and bisphenol-A-diglycidyl ether Asolution of 177 g of a technically manufactured bisphenol-A diglycidylether (Araldite MY 790) of high monomer content (5.70 epoxideequivalents/kg) (corresponding to 0.5 mol) in 500 ml ofdimethylformamide is mixed with 128.2 g of 5,5-dimethylhydantoin 1 mol)and the mixture is heated to 120C whilst stirring. 1.7 g oftetraethylammonium chloride are then added, whereupon a slightlyexothermic reaction commences. 1n the course thereof, the temperaturerises to 130C. Thereafter, the mixture is stirred for a further 2 hoursat 120C adjusted to pH=7 with a little strength sulphuric acid, filteredhot and concentrated at C/15 mm Hg. Thereafter the residue is dried toconstant weight at C/0.2 mm Hg. A solid, clear, light yellow adduct isobtained in quantitative yield. This crude adduct can be purified byrecrystallisation from 50% strength ethanol in the ratio 1:6. Afterdrying, 269.8 g (88.4% of theory) of a colourless fine crystallinematerial which melts at 169 182C is obtained. The NMR and IR spectrashow that predominantly an adduct of the following structure is present:

Adduct of methylene-bis-dimethylhydantoin and bisphenol-A diglycidylether 117.5 g of the bisphenol-A diglycidyl ether used in Example 2 (0.3mol) in 700 ml of dimethylformamide are reacted with 160 g ofl,1'-methylene-bis(5,5 dimethylhydantoin) (0.6 mol) at 124C, analogouslyto Example B. 0.9 g of tetraethylammonium chloride is used as thecatalyst. The reaction is again slightly exothermic After stirring for 3hours at 120C, the mixture is worked up according to Example B.

320 g of a yellowish, viscous resin, which is completely dried in vacuoat 70C, are obtained. A crude product which, according to NMR, agreeswith the structure shown below, is obtained. The elementary analysis ofthe crude product shows:

This product was again processed as it stands. n

YN -H EXAMPLE D Adduct of 5,5-dimethylhydantoin and(3,4-epoxycyclohexyl-methyl)3,4-epoxycyclohexanecarboxylate A solutionof 128 g of technically manufactured (3 ,4-epoxy-cyclohexylmethyl)-3,4-epoxycyclohexanecarboxylate (correspondingto 0.5 mol) in 300 ml of dimethylformamide is mixed, at 120C, with 1.7 gof tetraethylammonium chloride and 128.1 g of 5,5- dimethylhydantoin 1.0mol). The solution is stirred for 10 hours at 135C and is worked up asdescribed in Example B. A clear, light ochre-coloured product isobtained in quantitative yield; it can easily be powdered l5 andessentially corresponds to the following structure:

EXAMPLE F Adduct of bisphenol-A diglycid and 5 ,S-dimethyl-6-iso-propyl-5 ,6-dihydrouracil 3 l l 3 N N-ll H C C c L H C CH EXAMPLEE Adduct of 1,1-methylene-bis-dimethylhydantoin and3,4-epoxycyclohexylmethyl)-3,4-epoxycyclohexanecarboxylate Analogouslyto Example 1), 384 g of the epoxide resin used in Example D, in 2,000 mlof dimethylformamide, are reacted with 804.8 g of 1,1 '-methylene-bis(5,5-dimcthyl)-hydantoin, using 5 g of tetraethylammonium chloride asthe catalyst. The reaction is carried out analogously to Example D.Working up takes place as follows: The hot solution is filtered into anErlenmeyer flask and is left to stand at C. After some hours, the adductbegins to crystallise out. The mixture CH H C C 3 l CH H EXAMPLE GAdduct of higher'molecular bisphenol-A diglycidyl ether and5,5-dimethyl-6-isopropyl-5,6-dihydrouracil A mixture of 190 g of acommercially available high ermolecular bisphenol-A glycidyl ether resinwith 2.7 epoxide equivalents/kg (Araldite B), 94 g of 5,5-dimethyl-6isopropyl-5,6-dihydrouracil and 0.5 ml of 50% strength sodiumhydroxide solution is reacted at 150C, whilst stirring. After 1.5 hours,a sample taken from the batch shows an epoxide content of 0.39

is cooled at Whilst Stirring and 500 m1 of l are equivalent/kg. Themixture is then stirred for a further added, whereby a thlck crystalPaste results Thls 3 hours at 165C, in the course of which the epoxidetered and the product is suction-dried, and then dried t t drops t below0,1 e uivalent/kg, The adduct to constant weight at C under 25 mm Hg. Apale is poured out onto a metal sheet to cool. An adduct yellow crystalpowder is obtained, the yield being 1,048 mixture of predominantly thefollowing structure is obg (corresponding to 88.1% of theory). 69tained:

0 o H -N N CH C|HCH O @413 @4) cH cH cH N H N & HC 0 O H CH CH HCHC C/H.c l 3 3 3 3 I H H C In this formula, n denotes the average degree ofpolymerisation (also of the initial epoxide resin) of about 6.

EXAMPLE H Addition of ethylene oxide to the product from Example B 220 gof the adduct manufactured according to Example B (0.361 mol) and 1.4 gof lithium chloride are dissolved in 540 ml of dimethylformamide. Asolution of 43.7 g of ethene oxide (0.992 mol) in 250 ml ofdimethylformamide is added to the first solution at room temperature,whilst stirring gently. The mixture is warmed to 100C over the course of2 hours and stirred for a further 3 hours at this temperature.Thereafter it I is cooled to C, filtered and concentrated at C/20 mm Hg,and dried to constant weight at C/0.l mm Hg. 250 g of a clear, highlyviscous, light ochrecoloured polyol of theory) are obtained, of whichthe NMR spectrum agrees with predominantly the following structure:

EXAMPLE 1 Addition of ethylene oxide to the product from Example CAnalogously to Example H, a solution of 200 g of the adduct manufacturedaccording to Example C and 1.0 40

g of lithium chloride in 500 ml of dimethylformamide is treated, at roomtemperature, with a solution of 27.5 g of ethylene oxide in 100 ml ofdimethylformamide and the procedure described in Example H is followed.

g of a clear glassy tetraalcohol (95% of theory) are obtained and areglycidylated in the crude form.

EXAMPLE J Addition of ethylene oxide to the product from Example D 676 gof the adduct manufactured according to Example D are dissolved in 1,300ml of dimethylformamide. After addition of 1.7 g of lithium chloride,

234.5 g of ethylene oxide in 600 ml of dimethylformamide are added andthe procedure analogous to Example H is followed. 690 g of a product(87%) are obtained, in which the N-H groups of the formula given inExample D are very largely replaced by the structure NCH -CH -OH.

EXAMPLE K Adduct of 2 mols of 5,5-diethylbarbituric acid and 1 mol of3-( 3 ',4'-epoxycyclohexyl )-2,4-dioxaspiro-( 5 ,5 )-9, 10-epoxyundecane A solution of 64.3 g of technically manufactured 3- (3',4'-epoxycyclohexyl)-2,4-dioxaspiro-( 5 ,5 )-9 l 0- HC 0 3 CH3epoxyundecane (93.6% strength) (0.226 mol) and 0.75

A c c n l A 2 5 z 2 s 7 S cn o EXAMPLE 1 Adduct ofl,3-diglycidyl-5,S-dimethylhydantoin and 5,5-dimethylhydantoin 390.9 gof technically manufactured l,3-diglycidyl 5,5dimethylhydantoin (92.5%strength) (1.5 mols) and 5.0 g of tetraethylammonium chloride are dis l3l4 solved in 75 ml of dimethylformamide and this solution take placeanalogously to Example K. is stirred at l 10C. 384.5 g of5,5-dimethyl-hydantoin 44 g of the corresponding adduct are obtained inthe (3.0 mols) are then added with vigorous stirring. The form of alight powder (66.7% of theory). reaction becomes strongly exothermic sothat the heat- EXAMPLE mg bath 1S removed and replaced by an ice waterbath; 5 the temperature is thus regulated to 112C Adduct of1,1-methylene-bis(5,5-dimethylhydantoin) When the exothermic effect hassubsided, the mixture i is stirred for a further 3 hours at l 15C. Thesolvent is 11kmethylenebm3-g1yCldyL5jdlmethylhydamom) then distilled offat 100C/30 mm Hg and the product A miXtul'e 0f 205-5 g of y is dried at100c/0.2 mm Hg. 765 g of a pale yellow, y y y y epOXide q brittle glass,which can easily be Powdered, are oblemS/kg) (0'54 mol) 289's g oflll'methylene' mined bis(5,5-dimethyl-hydantoin) (1.08 mols), 1.8 g oftetraethylammonium chloride and 750 ml of dimethylformamide is stirredat 110 120C; the reaction becomes exothermic and is carried outaccording to Example K, and the product is worked up according toExample K.

488 g of a light yellow powder (98.6% of theory) are 335 g oftechnically manufactured l-glycidyl-3-Obtainedglycidyloxypropyl-5,S-dimethylhydantoin (epoxide EXAMPLE Pcontent 5.97 equivalents/kg) (1 mol) and 3.3 g oftetraethylammoniumchloride are dissolved in 1 litre of dimethylformamide and 258.2 g of5-isopropylhydantoin (2 mols) are added at 120C, whilst stirring. Thereac- A mixture of g of the liv'methylene'bis'w' tion becomes exothermicand the mixture is kept at g1yCidYl-5754imethy1hydantoinl q in 120C fora total of 5 hours by periodic cooling. Workample g oftetraiethylammomllm 9111mm and ing up takes place analogously to Example11 593 g 50.5 g of 6-methy1uracil (0.4 mol) 1S stirred for 10 hours at120C, whereby a clear, colourless solution 18 (theory: 583 g) of a hghtbrown powder memng at produced" this is worked up analogously to ExampleK. 486C (Mettler FP 51) are obtained. The elementary I 127 g (100% oftheory) of a light yellow, glassy submalysls of the Crude product Showsstance are obtained. This can be recrystallised from alcohol. 104 g(82.2% of theory) of fine crystals, melting at 176C (Mettler PF 51) areobtained.

EXAMPLE M Adduct of 5-isopropylhydantoin andlglycidyl-3-glycidyl-2-oxyn-propyl-5 ,5- dimethylhydantoin (molar ratio2:1

Adduct of 6methy1uraci1 and 1 ,1 '-methylene-bis-( 3-glycidy1-5,S-dimethylhydantoin) Found Calculated 7.3% H 7.3% H EXAMPLE Q I 97: N44 N Adduct of 5,5-dimethylhydantoin and 2,2 ,6,6-tetra(glycidylcarboxy-ethyl )cyclohexanone 123.8 g of2,2,6,6-tetra(glycidyl-carboxy-ethyl)- Accordmg to the H'NMR Spectrum,the crude product cyclohexanone (epoxide content: 5.9 equivalents/kg)only retains a trace of dimethylformamide. (0.184 mol), 94.1 g of5,5-dimethylhydantoin and 200 The product has the following structure:ml of dimethylformamide are stirred for 5 hours at 125 CH3; 3 CH3 CH/CH3org/ 0 o o CH,

CIH" H N N CH -CHCH -N N 2- 2 2N N H Y Y Y o o 0 55 I EXAMPLE N 130C;the reaction is initially slightly exothermic. Adduct of The working upof the product takes place analogously1,1-methylene-bis-(5,5-dimethyl-5,6-dihydrouracil) to Example K. 210 gof a highly viscous liquid are oband tained; this crude product stillcontains a trace ofdil-glycidyloxymethyl-3-glycidyl-5,S-dimethylhydantoin methylformamide.

l t' 2: 1 1 (mo ar ra 1o EXAMPLE R A so ution of 22.2 g ofl-glycidyloxymethyl-3- g1ycidyl 5a5 dimethylhydamoin (973% strength) 2:1adduct of lli3dlglycidyl5l; 5-d}:met{1yl-hydantom (0.077 mol) and 0.2 gof tetraethylammonium chloride ydrogenated eno in ml ofdimethylformamide is mixed, at C, with The following mixture is stirredfor 4.5 hours at 45.6 g of 1,1'-methylene-bis(5,5-dimethyl-5,6- 120C: 512.8 g of 1,3-diglycidyl-5,5dimethylhydantoin dihydrouracil) (0.154mol). The reaction, and working (2.0 mols), 240.4 g of hydrogenatedbisphenol A (1.0

manufacture of the tetraglycidyl compound.

HCI HC 0 /l l l 2:1 adduct of 5,5-dimethylhydantoin and the diglycidylether of hydrogenated bisphenol A MANUFACTURE OF THE POLYGLYCIDYLCOMPOUNDS ACCORDING TO THE INVENTION EXAMPLE (1) A mixture of 63.6 g ofthe adduct manufactured ac cording to Example A (0.1 mol; 0.4 equivalentof reactive H), 370 g of epichlorohydrin and 0.3 g oftetramethylammonium chloride is stirred for 140 minutes at 1 l7l 18C. Asample withdrawn from the batch and freed of all volatile constituentsthen contains 1.88 epoxide equivalents/kg.

The dehydrochlorination is carried out as follows: An azeotropiccirculatory distillation is set up, by application of vacuum (6090 mmHg) in such a way that a vigorous distillation proceeds in the reactionmixture at 60C. 38.4 g of strength sodium hydroxide solu tion (0.48 mol)are now added dropwise over the course of 150 minutes, whilst stirringvigorously. In the course thereof, the water present in the reactionmixture is continuously removed from the batch, and separated off.Thereafter, distillation is allowed to continue for a further 15minutes, the residue is cooled to 30C, and the sodium chloride producedin the reaction is filtered off. The filtrate is then washed with 50 mlof water to remove the last traces of caustic alkali and salt and theorganic phase is concentrated on a rotary evaporator at 60C/l5 mm Hg. 50ml of water are now added and traces of epichlorohydrin and the like aredistilled off together with this water. Thereafter, the same process isrepeated with 50 ml of toluene to remove remnants of water. The residueis then treated at 120C/0.2 mm Hg until it reaches constant weight.

82.7 g (96.2% of theory) of a brittle, clear, pale yellow resin ofepoxide content 4.30 equivalents/kg (92.7% of theory) are obtained. Thetotal chlorine content is l.l%. The new tetraglycidyl compound has asoftening point of 66C (according to Kofler) and essentially is presentin the following structure:

EXAMPLE (2) Glycidylation of the adduct according to Example BAnalogously to Example (1), 503 g of the adduct manufactured accordingto Example B (0.84 mol) are stirred with 2,495 g of epichlorohydrin(26.97 mols) and 5.6 g of tetraethylammonium chloride for 3 hours at C.Thereafter, dehydrochlorination is carried out, as described in Examplel with 350.5 g of 50% strength sodium hydroxide solution, underazeotropic circulatory distillation and whilst stirring vigorously.Working up and purification are also carried out analogously to Examplel 632 g (97% of theory) ofa very viscous tetraglycidyl compound areobtained, of epoxide content 4.26 epoxide equivalents/kg 86.4% oftheory).

EXAMPLE (3) Glycidylation of the adduct according to Example 1 179.8 gof the crude tetraalcohol manufactured ac cording to Example I (0.186mol) are treated with 552 g of epichlorohydrin (5.967 mols) and 0.9 g oftetraethylammonium chloride analogously to Example A. Thedehydrochlorination is carried out with 77.8 g of 50% strength sodiumhydroxide solution, again as described. After working up andpurification analogously to Example 1), 189.2 g of a very viscous,clear, light yellow tetraglycidyl compound (94% of theory) are obtained,of which the epoxide content is 3.4 epoxide equivalents/kg 100% oftheory). The total chlorine content is 2%.

EXAMPLE (4) Glycidylation of the adduct according to Example J 656.5 gof the tetraalcohol obtained according to Example J (1.1 mols) and 4 gof tetraethylammonium chloride in 3,330 g of epichlorohydrin (36.0 mols)are treated analogously to Example (1). The dehydrohalogcnation iscarried out with 456.6 g of 50% strength aqueous sodium hydroxidesolution (5.71 mols) in the manner described above. The working up againtakes place analogously to Example A. 704 g (78% oftheory) of thedesired tetraglycidyl compound,-of which the ep- 17 oxide content is4.69 epoxide equivalents per kg (95.8% of theory), are obtained. Thetotal chlorine content is 1.6%. The nitrogen content is 6.7% (theory,69%) EXAMPLE Glycidylation of the adduct from Example E 789 g of theadduct manufactured according to Example E (1 mol) together with 6.6 gof tetraethylammonium chloride are treated with 2,950 g ofepichlorohydrin according to Example (1). Both the dehydrochlorinationwith 410 g of 50% strength aqueous sodium hydroxide solution and thesubsequent working up are also carried out according to Example (1). 951g (95% of theory) of a solid, clear resin with 3.32 epoxideequivalents/kg (82.6% of theory) are obtained. The softening range isabout 92C.

EXAMPLE (6) Glycidylation of the adduct from Example F As described inExample l), 345 g of the adduct from Example F, 3.2 g oftetraethylammonium chloride, 1,420 g of epichlorohydrin and 199.5 g of50% strength aqueous sodium hydroxide solution are reacted, and workedup, under the conditions described.

383.2 g of the desired tetraglycidyl compound (94.8% of theory),containing 4.08 epoxide equivalents/kg (86% of theory), are obtained.The softening point is about 58C.

EXAMPLE (7) Glycidylation of the adduct from Example G 182 g of theadduct manufactured according to Example G are treated with 1.3 g oftetraethylammonium chloride and 1,200 g of epichlorohydrin according toExample (1). The dehydrochlorination with 67.3 g of 50% strength aqueoussodium hydroxide solution, and the further working up, also take placeas described above.

216.2 g ofa solid resin (99% of theory) with an epoxide content of 3.8equivalents/kg are obtained.

EXAMPLE (8) Tetraglycidyl compound of the product according to Example HAnalogously to Example l a solution of 139.4 g of the tetraalcoholmanufactured according to Example H (0.2 mol) is reacted with 444 g ofepichlorohydrin (4.8

mols) and 0.9 g of tetraethylammonium chloride by first stirring for 2hours at 90C.

Dchydrohalogenation is then carried out with 83.5 g of 50% strengthsodium hydroxide solution under azeotropic circulatory distillation, asdescribed in more detail in Example 1). The working up and purificationof the product take place according to Example 1 170.7 g of a yellow,clear, viscous resin (93.9% of theory), of epoxide content 4.35equivalents/kg (98.9% of theory), are obtained. The total chlorinecontent is 1.5%.

EXAMPLE (9) Tetraglycidyl compound of the product according to Example KA solution of 137.7 g of the adduct manufactured ac cording to ExampleK, of melting point 672C (0.217 mol) and 1.9 g of 50% strength aqueoustetramethyl- Found Calculated (C H N O 7.4% H 7.3% H 6.7% N 6.5% N

14% C1 0.0% Cl Example 10) Tetraglycidylation of the product accordingto Example 1 621 g of the adduct manufactured according to Example l(1.25 mols) are treated analogously to Example 1) with 3,700 g ofepichlorohydrin, 10 g of 50% strength aqueous tetramethylammoniumchloride solution and then with 460 g of 40% strength aqueous sodiumhydroxide solution (5.75 mols); the working up of the product is carriedout appropriately.

762.2 g (84.6% of theory) of a brown tetraglycidyl compound with 4.96epoxide equivalents/kg (89.3% of theory) and 1.2% of total chlorine,which softens at room temperature, are obtained.

EXAMPLE l l Tetraglycidylation of the product according to Example M Thefollowing substances are reacted analogously to Example 1): 563.0 g ofthe adduct from Example M (0.966 mol), 2,860 g of epichlorohydrin (30.9mols), 8.5 g of 50% strength aqueous tetramethylammonium chloride and356 g of 50% strength aqueous sodium hydroxide solution.

Working up takes place as described above and a highly viscous brownresin, of epoxide content 4.37 equivalents/kg (88.1% of theory), isobtained in 92% yield (715.7 g); the total chlorine content is 2%.

EXAMPLE (12) Tetraglycidylation of the product according to Example NThe following are reacted analogously to Example (1): 36 g of the adductfrom Example N (0.042 mol), 124 g of epichlorohydrin (1.34 mols), 0.7 gof 50% strength aqueous tetramethylammonium chloride and 15.4 g of 50%strength aqueous sodium hydroxide solution (0.19 mol).

After the customary working up, 28 g (62%) of a light brown, tacky resinare obtained. Epoxide content 3.08 equivalents/kg (83% of theory).

EXAMPLE (l3) Tetraglycidylation of the product according to Example 0The following are reacted according to Example (1): 0.315 mol of adductaccording to Example 0 (289 g),

19 1O mols of epichlorohydrin (925 g), 2.8 g of 50% strength aqueoustetramethylammonium chloride and 1.45 mols of 50% strength sodiumhydroxide solution (1 16 g). Working up takes place as mentioned and alight yellow, solid tetraglycidyl compound is obtained, of softeningpoint 67C (according to Kofier). The epoxide content is 3.71equivalents/kg (94.6% of theory).

EXAMPLE 14) Tetraglycidyl compound of the product according to Example CThe following were reacted analogously to Example (1 444.6 g of adduct,manufactured according to Example C (0.5 mol), 1,480 g ofepichlorohydrin (16 mols), 8.8 g of 50% strength aqueoustetramethylammonium chloride and 184 g of 50% strength sodium hydroxidesolution (2.3 mols).

The product is isolated according to Example 1) and 441.4 g (81%) of asolid, light brown resin are obtained, softening at 78C (Kofler) andhaving an epoxide content of 3.41 equivalents/kg (93.9% theory).

EXAMPLE (15) Tetraglycidyl compound of the product according to ExampleP The following are reacted analogously to Example (1): 72.0 g of theadduct according to Example P (0.114 mol), 474.0 g of epichlorohydrin(5.125 mols), 4.6 g of tetramethylammonium chloride, 50% strength inwater and 42.4 g of 50% strength aqueous sodium hydroxide solution (0.53mol).

The customary working up yields 76.0 g (77.9% of theory) of thetetraglycidyl compound of epoxide content of 3.81 equivalents/kg (81.5%of theory); the compound softens at 103C (Kofler).

EXAMPLE 16) Polyglycidyl compound of the product according to Example QEXAMPLE l7:

Glycidylation of the adduct manufactured according to Example R 736 g ofthe adduct manufactured according to Example R, having an epoxidecontent of 2.49 equivalents/kg 1 mol), are reacted with 2,738 g ofepichlorohydrin and g of 50% strength aqueous tetraethylammoniumbromide, the procedure according to Example I being followed, and thedehydrohalogenation being carried out with 197 g of 50% strength aqueoussodium hydroxide solution, in the manner described above.

Working up also takes place according to Example 1, and 302.3 g (36.3%of theory) of a clear, yellow resin 20 of medium viscosity, of which theepoxide content corresponds to 4.68 equivalents/kg (97.5% of theory),are obtained.

EXAMPLE l8:

Glycidylation of the adduct manufactured according to Example S Thefollowing are reacted analogously to the description in Example 1: 750 gof the adduct according to Example S (1 mol), 4,163 g of epichlorohydrin(45 mols), 20 g of tetraethylammonium chloride (50% strength, aqueous),and 400 g of 50% strength sodium hydroxide solution (5 mols).

Working up also takes place according to Example 1 and 810 g (97.2% oftheory) of a highly viscous resin of epoxide content 4.07 equivalents/kg(84.8% of theory) are obtained.

B EXAMPLES OF APPLICATIONS Example I 48 parts of the epoxide resinmanufactured according to Example 4), with 4.69 epoxide equivalents/kg,are mixed with 55 of hexahydrophthalic anhydride and stirred at C togive a homogeneous melt. This mixture is poured into aluminium moulds of4 mm wall thickness which have been prewarmed to C and is cured in 6hours at 100C and 2 hours at C and 10 hours at C. Mouldings having thefollowing properties are obtained:

Flexural strength (VSM 77,103) 15.816.8 kp/mm Deflection (VSM 77,103) 611 mm EXAMPLE I] 64 parts of the tetraglycidyl compound manufacturedaccording to Example 8), containing 4.35 epoxide equivalents/kg, aremixed with 37 parts of hexahydrophthalic anhydride at 80C and themixture is cured in an aluminium mould of 4 mm wall thickness in 4 hoursat 120C and 15 hours at C. A clear, transparent moulding having thefollowing properties is obtained:

Flexural strength (VSM 77,103) 15.8-17.2 kp/mm Deflection (VSM 77,103)810 mm Impact strength (VSM 77,105) 13.3 cmkp/cm Heat distortion pointaccording to Martens Water absorption (DIN 54,458) (4 days/20C) EXAMPLE111 100 parts of the epoxide resin obtained according to Example 1 1 aremixed with 75 parts of hexahydrophthalic anhydride at 80C to give ahomogeneous melt and the mixture is cured in an aluminium mould (4 mmsheets) in 4 hours/80C and 16 hours/140C. The mouldings thus obtainedhave the following mechanical properties:

Flexural strength (VSM 77,103) 16 kp/mm Heat distortion point accordingto Martens (DIN 54,458) 146-147C Water absorption (4 days/20C) 0.65?!vEXAMPLE IV -Continued l parts of the epoxide resin manufactured accord-CH. [:H 0 ing to Example 1 l are processed with 75 parts ofhexahydrophthalic anhydride as described in Example III, 7 I

and the mouldings obtained show the following proper- 2 ties: C Y ll OFlexural strength (VSM 77.103) l4-36 (mean value from 5 mcasurements=24)I kp/mm Hcut distortion point according to Maflcns (DIN 54 458) l l9l22CWater absorption (4 days/C) 0.6% I

EXAMPLE V 100 parts of epoxide resin from Example 9 are treated with 70parts of hexahydrophthalic anhydride according to Example Ill. Castingshaving the following 20 properties are obtained:

Flcxural strength (VSM 77,l03) 23.0 kp/rru'n Heat distortion pointaccording to Martens (DlN 54.458) l25l26C 25 Water absorption (4days/20C) 0.44%

(1 hour/ 100C) 041% wherein a and b are identical or different anddenote either 0 or l' Wh i 1 1s :1 i iii l com ound of the formula R; lshydrogen or methyl;

' p yg y y p and R is one of the radicals A CH CHCH R'CH -CH 7CH CH CHCH CH 2! 3 Z 2 o (I) l o cH ci\1 cH ior C CH 2 CH CH CH CH 2.Polyglycidyl compound according to claim 1 chawherein A is an organicradical of the formula racterised m that R 1n the formula II denotes oneof the radicals 0 CH1; CH:| CH3 CH3 0 40 n C ---C CH; CH! I I l -N N-(HN N CHC CH; CH.

ll (H, CH, 0 and II --c CHu v C /CH2-CH2\ H --N\ N(H.:-(TH() \CHFCH2 2 F3. Polyglycidyl compound of the formula H C H C H C H c CH3 3 CH 3 CH 3CH 3 t 3 3 3 o I l 0 /l /l H-1((H(H,- N N CH -(lZH-CH- N N cH, N NCH(lIH--CH. N N--CH2CHCH2 0 Y 1 Y E Y 2 2 o (11 o o C H o H L TH 23 4.Polyglycidyl compound of the formula I CH 24 5. Polyglycidyl compound ofthe formula Y n 0 W0

1. A POLYGLYCIDYL COMPOUND OF THE FORMULA
 2. Polyglycidyl compoundaccording to claim 1 characterised in that R2 in the formula II denotesone of the radicals
 3. Polyglycidyl compound of the formula 4.Polyglycidyl compound of the formula
 5. Polyglycidyl compound of theformula